TWI325858B - Method of purifying phenol - Google Patents

Description

1325858 发明, invention description: [Technical field to which the invention pertains] The present invention relates to a method for purifying phenol. [Prior Art] A method for producing phenol is to oxidize cumene to cumene hydroperoxide and to decompose cumene hydroperoxide by a splitting reaction to produce a reaction product of phenol and acetone. The phenol produced by this method may contain impurities or product contaminants that are not easily removed by conventional methods such as distillation. These impurities are not suitable because they cause the formation of colored products when the phenol is used for subsequent processing including gasification of phenol or sulfonic acid. The contaminant formed at the age of manufacture is a ketone. U.S. Patent No. 3,454,653 discloses the use of a synthetic cerium oxide-alumina catalyst which preferably contains from 5% to 3% by weight of alumina and from 95% to 70% by weight of cerium oxide. The cerium oxide-alumina catalyst can also be modified to contain Group VIA metals (e.g., chromium, turn or crane) in the range of 0.01 to 5% by weight of the catalyst. U.S. Patent No. 3,029,294 discloses the use of certain materials (tantalum alumina, aluminum niobate, ion exchange resins, mineral acids, strong organic acids, and surface active soils) in the desired treatment to form aliphatic alpha groups in the enzyme. The compound is converted to a stupid and furan. It is proposed to purify a product having a small amount of contaminant (e.g., _). [Explanation] It has surprisingly been found that an alcohol can be obtained by purity. This method of purification is high

Touch I, have low oxidized oxide content and include oxidized and VIA

O:\90\90950.DOC 1325858 Group metals. The present invention therefore provides a process comprising: 'it produces 27 phenols with a low cerium oxide content under contact conditions, as appropriate and still includes oxidative purification of the phenolic product, which includes phenol and a contaminating concentration of hydroxyketone. The contact with the VIA metal treatment catalyst is completed. [Embodiment] Under the condition that it is suitable to convert part of the contaminated compound into another compound, the test fluid and the simple touch are continuously treated by the Tunglong treatment fluid. The treatment catalyst is a (4) low-containing oxidative catalyst comprising a branch according to oxidation. Figure 1 is a diagram depicting a phenol purification reaction system and method. The phenolic product fluid to be treated or purified in accordance with the present invention may be any phenolic material having a small amount of contaminants. Such phenolic product fluids, including phenols and small amounts of contaminants, are up to 95% by weight of the product fluid up to 1%, and more preferably more than 98% by weight and more than 99% by weight. The concentration of contaminants in a good beta phenol product fluid is typically the concentration of a particular contaminant. Although the contaminant component of the product fluid may be any compound that imparts unsuitable properties to the fluid of the aged product, the contaminant compound is usually produced by the production of cumene hydroperoxide produced by decomposition of cumene. Those compounds. Such contaminants of a phenol product fluid are aliphatic carbonyl-based compounds such as, for example, hydroxy ketones. The concentration of contaminant of the phenolic product fluid to be treated or purified may range from a contamination concentration to 1 weight percent 'more generally 3 parts per million by weight (ppmw) to 1 〇, 〇〇〇 ppmw or 5 ppmw to 5000 ppmw. Most generally, the concentration of the contaminant will range from 1 〇〇 \ 90 \ 9 〇 95 〇 . D 〇 C -6 to 1325 858 ppmw to 2000 ppmw, and the purified phenol product or treated phenol product fluid may have a reduced To a contaminant/density lower than the concentration of contaminants in the phenol product fluid to be treated in accordance with the present invention. The contaminant contained in the phenolic product fluid is at least partially (most preferably) removed from the phenol product fluid or converted to a reaction product of another compound by the reaction. The reaction product is preferably separated from the phenol by a conventional distillation method than a contaminant. The concentration of contaminants in the purified or treated phenol product is a non-contaminating concentration typically less than or 10 ppmw. However, a concentration of 5 dyes of purified or treated phenol product fluid is less than or 5 paws rated as desired, but preferably less than 3 ppmw. Concentrated contaminants in purified or treated products have a small concentration of W or even the most undetectable concentration. The process of the present invention comprises producing or supplying a treated or purified desired product as described below after contacting the phenolic product fluid with a Group VIA metal composition having a low cerium oxide content supported by alumina under suitable contact conditions. Catalyst is an important concept of the present invention which provides a treated or purified phenol product having a reduced concentration of contaminants, but which additionally provides for the conversion of phenolic product fluid ketone contaminants without the formation of significant amounts of inappropriate benzofurans. As used in this specification, the term "benzophenone. South" includes not only the stupid substituted heterocyclic furan compound generally referred to as benzofuran, but also includes the group 3 such as mercaptobenzofuran, ethyl. Benzopyrene, dimethylbenzindole. A substituted benzofuran compound of south and diethylbenzofuran.仏 s, 'the concentration of benzofuran in the two treated phenols is generally determined by the amount of L ketone in the phenol product fluid to be treated. The concentration of benzoxanthene can be less than 5 pp Xiao appropriate low/agricultural degree to less than 2 Ppmw is preferred. Benzobite in the age to be treated

O:\90\90950.OOC 1325858 ° South) The agricultural degree is less than 1 ppmw. The process catalyst of the present invention comprises a VIA metal (Cr, Μ〇 _ on a oxide support having a low concentration of oxidized oxalate to provide the desired catalytic properties. When used in this specification, any Indicates that the concentration of oxidized oxide is "low or "small: or the plant is substantially absent" or similarly refers to the amount of oxidized rock in the treated catalyst compound at a concentration that is about low to provide the process of the present invention. Catalyst-catalyzed catalyst. In other words, the ketone contaminant of the product fluid is converted without forming a significant amount of benzofuran. Such cerium oxide concentration is less than 25 percent of the total weight of the treatment catalyst composition, but treated Preferably, the amount of oxidized stone is less than 10% by weight, and the total weight of the treatment catalyst is less than 5 weight percent of the oxidized oxide mass. However, the oxidized oxide content of the catalyst is less than 3 weight percent, which is optimal. The lower concentration limit of the oxygen cut in the treatment catalyst may be 〇1 wt% or 0.05 wt% or even 〇〇1 wt% of the total catalyst weight.

The preferred inorganic support for treating the catalyst composition is oxygen oxide and preferably the VIA metal is _ (preferably in the form of an oxide). The catalyst is treated in such a way that it has a low concentration of oxidized oxide (which is preferably substantially free of oxidized stones) and includes oxidized and lanthanum metals (e.g., molybdenum). The treatment of Benming's catalyst is prepared from a forged & composite comprising a via group of metals supported on an inorganic oxide support other than a oxidized stone or a material having a low cerium oxide content. The inorganic oxide building comprises solids which typically contain a majority of the alumina. Such materials are commonly referred to as refractory oxides and may include synthetic products as well as g-treated clays. Examples of possible synthetic refractory oxides include

O:\90\90950.DOC 1325858 Rolled aluminum, alumina-titanium oxide, alumina-magnesia' alumina-yttria and cerium oxide. The preferred inorganic oxide support is an alumina refractory oxide, i.e., a refractory oxide containing a substantial portion of alumina (at least 9 weight percent alumina). Any conventional catalyst grade alumina (including beta or gamma forms) can be used. Generally, the surface area of the inorganic oxide support is at least 10 m2/g', preferably in the range of from 25 m2/g to 800 m2/g. The Group VIA metal can be combined with the inorganic oxide support by any conventional means such as, for example, dry ion exchange, coprecipitation, infiltration, and the like. For example, 10-1 〇〇 mesh alumina can be infiltrated with an aqueous solution containing a VIA metal salt such as ammonium heptamolybdate or ammonium di-ammonate. In a preferred embodiment, the catalyst (including alumina and molybdenum oxide) of the present invention is mis-electrolyzed by aqueous solution molybdenum permeate permeating alumina. The aqueous solution of the molybdenum solution is composed of a water-soluble source of molybdenum oxide such as, for example, ammonium heptamolybdate or ammonium dimolybdate dissolved in water. Hydrogen peroxide can also be used to assist in the precipitation of the solution in some cases. For example, a molybdenum solution can be prepared by adding hydrogen peroxide in an amount of 1 to 1 mole of hydrogen peroxide per mole of molybdenum. Add a suitable soluble ammonia compound (such as monoethanolamine, propanolamine or ethylenediamine) to the molybdenum solution as needed to assist in the stability of the solution. After infiltration, the resulting material is dried and calcined. Drying is done in a traditional way. It can be dried by forced air drying, vacuum drying, air drying or similar methods. The drying temperature is not critical and depends on the particular method used for drying. A typical range of drying temperatures is 50. (: to 150. (: After drying, the material is calcined to produce the final treatment catalyst. The material can be calcined in an oxidizing or neutral atmosphere.) The tube is preferably in air. However, if 〇: '90 \90950 D〇c 1325858 Using a binder and/or lubricant, the material is heated in an oxygen-containing atmosphere (preferably in air) to burn off the binder and lubricant. The typical range of calcination temperature is 3 〇〇. 600 c. The burnout temperature depends on the oxygen concentration in the burnout atmosphere and the burnout time. Typically, the burnout temperature ranges from 3 〇〇 to lt. t to 6 〇 (rc. Dry, calcined and burnt) It can be combined into one or two steps. The combination of calcination and burnout is most often carried out using an oxygen-containing atmosphere. The treatment catalyst typically contains from 1 to 18 weight percent of the Via metal, from 5 to 15 weight percent. Preferably, it is from 6 weight% to 12 weight percent. The processing conditions of the phenol product fluid in contact with the treatment catalyst are such factors as the specific contaminants and contaminant concentrations contained in the phenol product fluid and the amount of removal required. Wheatification. The method of the invention is particularly advantageous The ketone can be effectively removed using moderate processing conditions without producing a large amount of inappropriate benzopyrene. The contact temperature can be in the range of 50 ° C to 25 (TC), with 9 (TC to 23 (TC is preferred) Between 1 ° C and 210 ° (best. Although the phenolic product fluid is not a necessary feature of the invention when it is in contact with the treatment catalyst, it is substantially liquid phase suitable. Thus, contact pressure In order to make the product fluid substantially liquid and up to 1 psig (700 kPa), the contact pressure is preferably in the range of from 1 psig to 6 psig. The phenol product fluid is by any suitable method known to the art. The catalyst contact is treated, but the contact occurs preferably in the reaction zone. The contacting can be a batch processing step or a relatively continuous processing step. In the latter operation, a solid bed for treating the catalyst or a catalyst can be applied. Moving bed or fluidized bed for treating catalyst. However, the contacting step is in the delineation of the reaction zone and contains the treatment catalyst.

O:\90\90950.00C -10- 1325858 The reaction vessel in the bed is preferably carried out. As such, the reaction vessel provides a means to contact the phenolic product fluid with the processing catalyst under suitable contact conditions (e.g., as described herein) and to produce a treated hydrazine product fluid. The flow rate of the phenol product fluid into the reaction zone is such that the hourly space velocity weight ("WHSV") is in the range of greater than zero to 1000 hours-丨. The term "space velocity weight per hour" as used in this specification refers to the ratio of the rate at which the product fluid is loaded into the reaction zone per hour divided by the number of pounds of processing catalyst contained in the reaction zone. The phenol product fluid loaded into the reaction zone may preferably be in the range of from 0.1 hour to 1 hour to 1 hour in 0.1 hour to 1 hour to 1 hour, and preferably from 0.25 hour to 1 to 25 hours. Referring now to Fig. 2, there is shown a phenol purification reaction system 1 including a reactor 12. Reactor 12 delineates the reaction zone containing treatment catalyst 14. The reactor is equipped with an injection port 16 and a discharge port 18 and provides a method of contacting the treatment fluid 14 with a phenolic fluid having a contaminating concentration of ketone under appropriate contact conditions to convert a portion of the ketone to another compound. The phenolic fluid product is introduced into the reaction zone defined by reactor 12 by means of a conduit 2 which is operatively connected to the injection port to provide a fluid flow associated with the reaction zone. The purified phenol fluid is produced as a means of passing through the discharge vents of the outlet 18 and the conduit 22. Conduit 22 is operatively coupled to discharge port 18 to provide fluid flow contact with the reaction zone. EXAMPLES Examples 1-4 describe the measurement of the efficiency of the oxidation of a low oxidized oxide content in the treatment of a phenol product containing a contaminant concentration of hydroxyketone, particularly when such = (d) is used as a binder in combination with molybdenum. These examples show that an oxidized chain with a low oxygen oxide content can be effectively used to contain the four products.

〇\W)\9〇9SO.DOC -11 - 1325858 without excessive production of benzofuran by-products. In the following examples i·4, the pure, anhydrous phenol collected in the product fluid was taken from the side of the distillation tube using the isopropylbenzene. The raw material supply for each of the examples was prepared by adding a small amount of ketone impurities using the available reactants. The phenolic feedstock is then supplied at a temperature of 50-150 by stirring in the liquid phase with a 2% by weight based on the weight of the phenol. (: contact at a temperature for a period of time. The reaction product mixture is then cooled, filtered and analyzed by gas chromatography for individual ketones and corresponding benzofuran derivatives. The alumina used for the catalyst is less than 3 weight percent. Cerium oxide. Example 1 (8% heart containing 1-2% dispersed oxidized oxide oxidized sulphate 7 oxidized) containing 990 PPm hydroxyacetone (HA or acetol), 52 〇 ppm hydroxy 2-butanone (1HB And a feedstock of 490 ppm 3-hydroxy-2-butanone (3HB or acetamyl methanol) was prepared from pure phenol and contacted with an alumina catalyst containing about 8 percent molybdenum for 2 hours at 145. Catalyst pre-activated And dry. The average ketone conversion of η a , 1HB and 3HB in the three separate experiments was 98, 98 and 1 〇〇 respectively. About 6% of HA was converted to 2-methylbenzofuran, 3%. Conversion to 2·ethylbenzofuran, and 3% of 3_hb is converted to hydrazine, 3 dimethylbenzofuran. Example 2 (4% Mo on 7 alumina containing 1 _2% dispersed cerium oxide) 990 Phenol by base acetone or propanol), 52〇ppm丨_hydroxy 2·butanone (1HB) and 490 ppm 3_hydroxy-2-butanone (3HB or acetamylmethyl sterol) The feed was prepared from pure phenol and contacted with an oxidation catalyst containing about 4 percent molybdenum for 2 hours at l45»c. The catalyst is preactivated and dried. The average ketone conversion of HA, 1HB and 3HB in the three separate experiments was 84, 87 and 98, respectively. The corresponding benzopyrenes have an average selectivity of about 6, 3, and 25 percent. 0\90^90950.〇〇c -12- 1325858 Example 3 (Alumina only) Raw materials containing 990 ppm HA, 520 ppm 1HB and 49〇 p_ 3hb are prepared from pure powder and are in! The 451 was contacted with a pre-activated and dried indium-free oxidizing catalyst for 2 hours. The ketone conversion rates of HA, Cong and 3HB were ^, 15 and 8 percentages, respectively. The corresponding benzofuran selectivity is about 25 and 280. 77 Example 4 (blank-heated but no catalyst) Contains 990 ppm HA ' 520 ppm 1HB& 49〇 ppm 3hb of raw material supply Prepared from pure phenol and at 丨45. (: Heating with no catalyst for 2 hours. The average ketone conversion of HA, 1HB and 3HB in three separate tests was 5, 5 and 7 respectively. The benzofuran selectivity was about 3, 〇1 and 3 on average. Percentage. The following table summarizes the results of the above test. ^_1"Use different catalysts to control the rate of 8% Mo on the oxidation

The conversion data presented in Table I above shows that the use of low cerium oxide content alumina or molybdenum supported on low cerium oxide alumina in the treatment of small hydroxy ketone containing phenolic products with or without treatment catalysts More than the advantages. As can be observed, the conversion rate of the catalyst used is better than that of the catalyst. The selectivity to benzopyrene is also very low, in most cases it is 3 percent Λ or less. (4) Oxidation (10) provides U with an oxidized catalyst significantly better than q\9〇\9095〇· 〇〇^ • 13· 1325858 Good hydroxy ketone conversion, and the molybdenum/alumina catalyst still provides low selectivity to benzofuran. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram for describing a phenol purification reaction system and method. [Description of symbolic representation] 10 Phenol purification reaction system 12 Reactor 14 Treatment catalyst 16 Injection inlet 18 Discharge port 20 Catheter 22 Catheter O:\90\90950.DOC -14-

Claims (1)

132585| __4 Special Office Please apply for a patent scope replacement in Chinese (93⁄4% day repair (more) original copy, Shen Qing patent range A method comprising: purifying a phenol product comprising a phenol and a contaminating concentration of hydroxyketone by contacting the phenolic product with a treatment catalyst under suitable contact conditions comprising a temperature range of up to 25 ΟX: The treatment catalyst is composed of alumina, the oxide catalyst of 0.01% by weight to 25% by weight based on the total weight of the treatment catalyst. 2. If you apply for a patent scope! The method of the present invention, wherein the content of the product is in the range of 95% by weight to 1% by weight, and the pollution wave is in the range of more than 3 ppmw. 3. The method of claim 2, wherein the contact condition comprises a contact pressure of up to 690 kPa (100 pSig). 4. The method of claim 13 wherein the amount of indium present in the treatment catalyst ranges from 1 weight percent to 8 weight percent of the treatment catalyst. 5. The method of claim 3 Wherein the amount of molybdenum present in the treatment catalyst is in the range of from 1 weight percent to 18 weight percent of the treatment catalyst. 6. A method of purifying a phenol fluid according to the scope of the patent application, comprising: providing a reactor having an injection port and a discharge port and defining a reaction zone containing a treatment catalyst, the treatment catalyst being alumina, The treatment catalyst comprises 0.01% to 25% by weight of cerium oxide and molybdenum; the phenol fluid is introduced into the reaction zone through the injection port; and the reaction zone is operated under the appropriate reaction conditions to convert the phenol Fluid 90050-990115.doc 1325858 • At least a portion of the ketone is the other compound; and the purified helium fluid is removed from the reaction zone through the discharge port as a reactor effluent. The method of claim 1 or 6, wherein the treatment catalyst has an oxidized dream content of _wt% by weight based on the total weight of the treatment catalyst. The heart of the law, which makes the total weight of the treatment Liu * & Λ. Ten is 〇. 〇 1% by weight to 5 weights yo The cerium content of the catalyst. 9. The method of claim 1 or 6 of the method of treating the total weight of the catalyst, wherein the treatment of the shoulder content of the catalyst. 〇·01% by weight to 3 weights 90950-990115.doc